1. Field of the Invention
The invention relates to cementitious dry mortars modified with a polymer powder composition and to their use as adhesives and coating materials.
2. Background Art
Mixtures of cement and water-redispersible polymer powders are known. The redispersible powder is added as an organic binder to improve adhesion to the substrate and the flexibility of the cured or xe2x80x9csetxe2x80x9d mixture. Further ingredients of these mixtures include fillers and also thickeners for controlling the rheological properties. Conventional additives also include dispersants, cement plasticizers, and additives for accelerating or retarding the setting of the cement. One example of a mortar base mix is disclosed in DE-A 1951171.
Water-containing, settable mixtures are prepared by admixing the dry components with water, and are then used, for example, in construction adhesives, troweling compositions, reinforcing mortars for exterior insulation and finish systems, and as adhesives for bonding wood flooring. Such compositions have a relatively short pot life, which depending on application, may range from a fraction of an hour up to several hours. The disadvantage of this relatively short pot life is that mortars which cannot be processed promptly are no longer useable and must therefore be disposed of. Especially when cementitious compounds are being processed by machine, the short pot life may result in premature solidification of the material in the machine and its consequent blockage.
In order to delay the setting of cementitious compounds, retardants are frequently used. Retardants have been selected from hydroxycarboxylic acids or dicarboxylic acids or salts thereof, as well as saccharides. Examples include oxalic acid, succinic acid, tartaric acid, gluconic acid, citric acid, sucrose, glucose, fructose, sorbitol and pentaerythritol. Further examples of retarders are polyphosphates, metaphosphoric acid, and borax. A disadvantage associated with the use of such retardants is that although the cement compound remains processable, the water resistance of the set mixture is greatly decreased.
From EP-A 338293 it is known that the mode of action of cement plasticizers based on olefin-maleic anhydride copolymers may be improved by combination with zinc oxide, since complexation of the copolymers with zinc ions prevents the formation of ineffective, water-soluble olefin-maleic acid copolymers by hydrolysis of the anhydride functionality.
It is an object of the invention to modify cementitious mortar compounds so that their setting is effectively retarded, without significant reduction in the water resistance of the set cement compositions. These and other objects are achieved by providing a dry cementitious mortar mix which contains, in addition to conventional ingredients, a redispersible polymer powder and a most minor quantity of specific zinc compounds, preferably also in conjunction with an alkali metal or alkaline earth metal hydroxide.
The invention provides cementitious dry mortars comprising
a) from 0.5 to 80% by weight of cement,
b) from 0 to 97% by weight of fillers,
c) from 0 to 3.5% by weight of thickeners, wherein a polymer powder composition is present, with
d) from 1.0 to 80% by weight of redispersible polymer powder,
e) from 0.02 to 4.0% by weight of one or more compounds from the group consisting of zinc oxide, zinc hydroxide, and zinc hydroxide carbonate,
f) from 0 to 30% by weight of alkali metal hydroxide and/or alkaline earth metal hydroxide,
based in each case on the overall weight of the dry mortar, the percentages by weight adding up to 100% by weight.
The cement fraction a) is preferably from 0.5 to 40% by weight, with particular preference from 8 to 16% by weight. Preference is given to using Portland cement.
Suitable fillers b) are quartz sand, quartz flour, calcium carbonate, dolomite, aluminum silicates, talc or mica, or else lightweight fillers such as pumice, foamed glass, aerated concrete, perlites or vermiculites. Mixtures of said fillers may also be used. The filler fraction is preferably from 10 to 90% by weight, with particular preference from 75 to 90% by weight.
Examples of thickeners c) are polysaccharides such as cellulose ethers and modified cellulose ethers, starch ethers, guar gum or xanthan gum, phyllosilicates, polycarboxylic acids such as polyacrylic acid and the partial esters thereof, polyvinyl alcohols, which optionally have been acetalized and/or hydrophobically modified, casein, and associative thickeners. It is also possible to use mixtures of these or other thickeners. Preference is given to the cellulose ethers, modified cellulose ethers, optionally acetalized and/or hydrophobically modified, polyvinyl alcohols, and mixtures thereof. It is preferred to use from 0.05 to 2.5% by weight, with particular preference from 0.05 to 0.5% by weight, of thickeners.
Water-redispersible polymer powders d) are those which in water break down into primary particles, which are then dispersed (xe2x80x9credispersedxe2x80x9d) in water. Suitable polymers include those based on one or more monomers from the group embracing vinyl esters of unbranched or branched alkylcarboxylic acids having from 1 to 15 carbon atoms, methacrylic esters and acrylic esters of alcohols having from 1 to 10 carbon atoms, vinyl aromatics, olefins, dienes, and vinyl halides. It is also possible to use mixtures of these polymers. Preference is given to using from 1 to 10% by weight of water-redispersible polymer powders d).
Preferred vinyl esters are vinyl acetate, vinyl propionate, vinyl butyrate, vinyl 2-ethylhexanoate, vinyl laurate, 1-methylvinyl acetate, vinyl pivalate, and vinyl esters of alpha-branched monocarboxylic acids having from 5 to 11 carbon atoms, examples being VeoVa5R, VeoVa9R, VeoVa10R or VeoVa11R (trade names of Shell). Preferred methacrylic esters or acrylic esters are methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, n-butyl acrylate, n-butyl methacrylate, and 2-ethylhexyl acrylate. Preferred vinylaromatics are styrene, methylstyrene, and vinyltoluene. A preferred vinyl halide is vinyl chloride. The preferred olefins are ethylene and propylene, and the preferred dienes are 1,3-butadiene and isoprene.
If desired, the polymers may also contain from 0.1 to 10% by weight, based on the overall weight of the polymer, of functional comonomers. These functional comonomers may include ethylenically unsaturated monocarboxylic or dicarboxylic acids such as acrylic acid; ethylenically unsaturated carboxamides such as (meth)acrylamide; ethylenically unsaturated sulfonic acids and/or their salts, preferably vinylsulfonic acid; polyethylenically unsaturated comonomers, examples being divinyl adipate, diallyl maleate, allyl methacrylate and triallyl cyanurate; and/or N-methylol (meth)acrylamides and their ethers, for example their isobutoxy or n-butoxy ethers.
Particularly preferred polymers are those listed below, the weight percentages adding up to 100% by weight together where appropriate with the fraction of functional comonomer units:
From the group of the vinyl ester polymers: vinyl acetate polymers; vinyl acetate-ethylene copolymers with an ethylene content of from 1 to 60% by weight; vinyl ester-ethylene-vinyl chloride copolymers with an ethylene content of from 1 to 40% by weight and a vinyl chloride content of from 20 to 90% by weight; vinyl acetate copolymers with from 1 to 50% by weight of one or more copolymerizable vinyl esters such as vinyl laurate, vinyl pivalate, vinyl esters of an alpha-branched carboxylic acid, especially Versatic acid vinyl esters (VeoVa9R, VeoVa10R, VeoVa11R), which may also contain from 1 to 40% by weight of ethylene; and vinyl acetate-acrylic ester copolymers with from 1 to 60% by weight of acrylic ester, especially n-butyl acrylate or 2-ethylhexyl acrylate, and which may also contain from 1 to 40% by weight of ethylene.
From the group of the (meth)acrylic ester polymers: polymers of n-butyl acrylate or 2-ethylhexyl acrylate; copolymers of methyl methacrylate with n-butyl acrylate and/or 2-ethylhexyl acrylate; and copolymers of methyl methacrylate with 1,3-butadiene.
From the group of the vinyl chloride polymers: besides the abovementioned vinyl ester/vinyl chloride/ethylene copolymers, vinyl chloride-ethylene copolymers and vinyl chloride-acrylate copolymers.
From the group of the styrene polymers: styrene-butadiene copolymers and styrene-acrylic ester copolymers such as styrene-n-butyl acrylate or styrene-2-ethylhexyl acrylate, each with a styrene content of from 10 to 70% by weight.
The polymers are prepared in a conventional manner, preferably by the emulsion polymerization process. The dispersions used may be stabilized with emulsifier or else with a protective colloid, an example being polyvinyl alcohol. To prepare the water-redispersible polymer powders, the polymer dispersion obtainable in this way is dried. Drying may be effected by means of spray drying, freeze drying, or by coagulation of the dispersion and subsequent fluidized bed drying. Preference is given to spray drying.
The zinc compounds e) are used preferably in an amount of from 0.02 to 2% by weight, with particular preference from 0.05 to 0.5% by weight. It is preferred to use zinc oxide.
As component f), preference is given to the alkaline earth metal hydroxides, especially calcium hydroxide. Component f) is used preferably in an amount of from 0.1 to 10% by weight, with particular preference from 0.1 to 4% by weight.
Most preferred are compositions comprising
a) from 8 to 16% by weight of Portland cement,
b) from 75 to 90% by weight of one or more fillers from the group consisting of calcium carbonate and/or quartz sand,
c) from 0.05 to 0.5% by weight of one or more thickeners from the group consisting of cellulose ethers, modified cellulose ethers, polyvinyl alcohols, acetalized and/or hydrophobically modified polyvinyl alcohols,
d) from 1 to 10% by weight of redispersible powders based on one or more monomers from the group consisting of vinyl esters of unbranched or branched alkylcarboxylic acids having from 1 to 15 carbon atoms, methacrylic esters and acrylic esters of alcohols having from 1 to 10 carbon atoms, vinylaromatics, olefins, dienes, and vinyl halides,
e) from 0.05 to 0.5% by weight of zinc oxide, and
f) from 0.1 to 4% by weight of calcium hydroxide, the sum of the percentages by weight being 100 percent relative to these components.
The composition is generally prepared by mixing components a) to f) to a dry mortar in conventional powder mixers and homogenizing the mixture. The amount of water needed for processing to mortar compounds is added prior to processing. Another possible procedure is to stir the individual components a) to f) separately with water to give a mortar compound.
A further possible procedure is to prepare the cementitious mortar compounds using a formulated redispersible powder additive which includes one or more compounds e) from the group consisting of zinc oxide, zinc hydroxide and zinc hydroxycarbonate and also, if desired, thickeners c) and/or, if desired, alkali metal hydroxide and/or alkaline earth metal hydroxide. The formulated redispersible powder additive preferably contains from 0.5 to 50% by weight of component e), from 0 to 200% by weight, with particular preference from 1 to 200% by weight, of component f), and 0-50% by weight, with particular preference from 0.5 to 50% by weight, of component c), based in each case on the weight fraction of the redispersible powder.
The cementitious mortar compounds obtainable in this way are suitable as adhesives, preferably construction adhesives, particularly as tile adhesives and as adhesives for bonding insulating panels and soundproofing panels. Further applications include that as a reinforcing compound for exterior insulation and finish systems, as a troweling compound, as a grout and as a coating compound (plaster). The cementitious mortar compounds are also suitable for bonding wood and wood materials, for example, to insulating panels.
The composition of the invention gives cementitious compounds which, in contrast to the use of conventional retardants, remain processable over several days without a loss in water resistance after hardening. This effect may be increased still further by including Ca hydroxide in the composition.